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CN106030408A - Composition for forming upper-layer resist film, and method for manufacturing semiconductor device using said composition - Google Patents

Composition for forming upper-layer resist film, and method for manufacturing semiconductor device using said composition Download PDF

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Publication number
CN106030408A
CN106030408A CN201580008682.3A CN201580008682A CN106030408A CN 106030408 A CN106030408 A CN 106030408A CN 201580008682 A CN201580008682 A CN 201580008682A CN 106030408 A CN106030408 A CN 106030408A
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upper layer
resist
layer film
compositions
formula
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CN106030408B (en
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藤谷德昌
坂本力丸
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

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  • Materials For Photolithography (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

[Problem] To provide a composition for forming a upper-layer resist film used in a lithography process during a step for manufacturing a semiconductor device, the composition not intermixing with the resist, and blocking exposure light, such as UV or DUV, that is undesirable particularly during EUV exposure, and selectively transmitting only EUV. The composition is capable of being developed using developing fluid after exposure. A composition for forming an upper-layer resist film including the unit structure represented in formula (1) and formula (2) shown below, and including: a polymer (P) having a weight-average molecular weight of 500-2000 according to GPC; and, as a solvent, a C8-16 ether compound.

Description

The semiconductor device of resistant upper layer film formation compositions and use said composition Manufacture method
Technical field
The present invention relates to use in make use of the manufacturing process of semiconductor device of photoetching, for reducing by exposure light The harmful effect that brings, obtain good Resist patterns effective photoetching resistant upper layer film formation compositions, and The Resist patterns using this photoetching resistant upper layer film formation compositions forms method, and employs this forming method The manufacture method of semiconductor device.
Background technology
All the time, in the manufacture of semiconductor device, carry out employing the microfabrication of photoetching technique.Above-mentioned fine add Work is following processing method: form the thin film of photo-corrosion-resisting agent composition on the processed substrates such as silicon wafer, has half via description The mask pattern of the pattern of conductor device is to this thin film irradiation ultraviolet radiation isoreactivity light, and develops, photic by gained The processed substrates such as silicon wafer are etched processing by Resist patterns as protecting film (mask).In recent years, quasiconductor dress The high integrationization development put, the active ray used also swashs to ArF quasi-molecule from KrF excimer laser (wavelength 248nm) Light (wavelength 193nm) short wavelengthization.Accompanying with this, the diffuse-reflectance from substrate of active ray, the impact of standing wave become asks greatly Topic, as undertaking the resist lower membrane of effect preventing reflection between photoresist and processed substrate, widely used The method that bottom surface antireflection film (Bottom Anti-Reflective Coating, BARC) is set.
As antireflection film, it is known that inorganic anti-reflective film such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, and bag Organic anti-reflective film containing light absorptive material Yu macromolecular compound.The former needs vacuum deposition apparatus, CVD to fill when film is formed Put, the equipment such as sputter equipment, on the other hand, the latter is favourable in terms of need not special equipment, thus has carried out a large amount of Research.
In recent years, follow-on as bearing after employing the photoetching technique of ArF excimer laser (wavelength 193nm) Photoetching technique, the ArF immersion photoetching technique being exposed via water is practical.But make the photoetching technique used up just welcome pole Limit, as the new photoetching technique that ArF immersion photoetching technique is later, uses the EUV lithography technology of EUV (wavelength 13.5nm) to be subject to Pay close attention to.In the semiconductor device manufacturing process employing EUV lithography, the substrate being coated with EUV resist is irradiated EUV and enters After row exposure, utilize developer solution to develop, thus form Resist patterns.
Disclose following method: in order to protect the impact of EUV resist the most contaminated material, block undesirable lonizing radiation, Such as UV, DUV (the outer radiation of OUT of BAND/ band, OOB), comprise polymer, described polymer bag on the upper strata of EUV resist Containing containing more than one the group (patent documentation 1, patent documentation 2) in beryllium, boron, carbon, silicon, zirconium, niobium and molybdenum.
Additionally, in order to block OOB, have the coating of the upper strata of EUV resist by polycarboxylated styrene (PHS) based compound, The top coat that acrylic compounds etc. are formed reduces OOB (non-patent literature 1)；On the upper strata of EUV resist, coating becomes The film of EUV resolution enhanced layer, absorbs OOB and makes the example (non-patent literature 2) that EUV resist resolution improves, but public affairs Open what kind of compositions most suitable.In addition the naphthalene-ring containing novolaks based material of bag is disclosed as on EUV lithography resist Tunic is formed with compositions (patent documentation 3).
It addition, as there is in immersion photoetching most suitable hydrophobicity and the resist of alkaline aqueous solution can being dissolved in Upper strata protecting film, discloses the resist-protecting membrane material of the acrylic polymer comprised containing hexafluoro isopropyl alcohol radical (specially Profit document 4)；Use the ester compounds with fluoroalkyl as the resist-protecting membrane material (patent documentation 5) of solvent；Comprise tool There is photoresist upper layer film formation compositions (patent documentation 6) of the solvent of ether structure；Comprising can be as at light Cause resist coated thereon immersion technique top coat or above antireflection film (Top Anti-Reflective Coating, TARC) the hexafluoro ethanol unit used and the top coat material (patent documentation 7) of alcohol series solvent.
It addition, disclose containing making there is carboxyl and/or sulfonic repetitive and the repetitive copolymerization comprising hydrocarbon The resist-protecting membrane material (patent documentation 8) of macromolecular compound.
Disclose polymer contain 50 moles of more than % containing at least appointing in aromatic group and heteroaromatic group The forming method (patent documentation 9) of the Resist patterns of the cellular construction of one.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-348133 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-198788 publication
Patent documentation 3: International Publication WO2012/053302 pamphlet
Patent documentation 4: Japanese Unexamined Patent Publication 2006-70244 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2007-241053 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2012-103738 publication
Patent documentation 7: Japanese Unexamined Patent Application Publication 2008-532067 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2008-065304 publication
Patent documentation 9: Japanese Unexamined Patent Publication 2013-228663 publication
Non-patent literature
Non-patent literature 1:Shimizu, M., Maruyama, K., Kimura, T., Nakagawa, H., Sharma, S., “Development of Chemically Amplified EUV resist for 22nm half pitch and beyond”Extreme Ultraviolet Lithography Symposium,Miami,(Oct,2011)
Non-patent literature 2:Proc.of SPIE Vol.7969 796916-1
Summary of the invention
Invent problem to be solved
As it has been described above, particularly when EUV resist is exposed, the EUV light of irradiation while radiation EUV light, Also radiation UV light, DUV light.That is, this EUV light is in addition to comprising EUV light, and the wavelength also comprising about 5% is below 300nm's Light, and the wavelength region intensity near such as 180nm～300nm, particularly 180nm～260nm is the highest, causes EUV resist Sensitivity decrease, the deterioration of pattern form.If live width becomes below 22nm, then this UV light, DUV light (OUT of BAND/ The outer radiation of band, OOB) impact occur, the resolution of EUV resist is brought harmful effect.
In order to remove the wavelength light near 180nm～260nm, also there is the method that light filter is set in a lithography system, but Exist and in operation, become complicated such problem.
The present invention is to provide for the most suitable resistant upper layer film formation combination for solving above-mentioned various problem Thing and make, the present invention provide manufacture semiconductor device photoetching process used in resistant upper layer film is formationed combine Thing, said composition, as resistant upper layer film, especially as the upper layer film of EUV resist, does not mixes with resist, particularly Undesirable exposure light such as UV, DUV is blocked and only selective transmission EUV, to the degassing from resist when EUV exposes Barrier excellent, developing liquid developing can be used after exposure, all can be suitable for for eurymeric resist or negative resist.
For the method solving problem
That is, the present invention is as follows.
[1] a kind of resistant upper layer film formation compositions, it comprises polymer (P) and the carbon number 8 as solvent ～the ether compound of 16, described polymer (P) is containing the cellular construction shown in following formula (1) and formula (2) and utilizes gel infiltration The weight average molecular weight that chromatography records is 500～2,000.
(in formula (1) or formula (2),
R1And R2Identical or different, represent hydrogen atom or the alkyl of carbon number 1～10,
Q1And Q2Identical or different, represent singly-bound, ester bond (-C (=O)-O-or-O-C (=O)-) or amido link (-NH-CO-or-CO-NH-),
X2Represent singly-bound, the alkylidene of carbon number 1～6 or the arlydene of carbon number 6～14,
R1aRepresent the alkyl of carbon number 1～10,
N1 represents the integer of 1～3, and m1 represents the integer of 0～2.〕
[2] compositions as described in [1], above-mentioned polymer (P) contains the cellular construction shown in following formula (3) further.
(in formula (3),
R3Represent hydrogen atom or the alkyl of carbon number 1～10,
Q3Represent singly-bound, ester bond (-C (=O)-O-or-O-C (=O)-) or amido link (-NH-CO-or- CO-NH-),
X3Represent singly-bound, the alkylidene of carbon number 1～6 or the arlydene of carbon number 6～14,
R3aIdentical or different, represent hydrogen atom, the alkyl of carbon number 1～10 or the acyl group of carbon number 1～4.〕
[3] compositions as described in [1], above-mentioned polymer (P) contains the cellular construction shown in following formula (4) further.
(in formula (4),
R4Represent hydrogen atom or the alkyl of carbon number 1～10,
Q4Represent singly-bound, ester bond (-C (=O)-O-or-O-C (=O)-) or amido link (-NH-CO-or- CO-NH-),
R4aRepresent that alkyl or the hydrogen of part or all of carbon number that can be replaced by fluorine atoms 1～10 of hydrogen atom are former The aryl of part or all of carbon number 6～14 that can be replaced by this alkyl of son.〕
[4] compositions as according to any one of [1]～[3], above-mentioned polymer (P) comprise further above-mentioned formula (3) and Cellular construction shown in formula (4).
[5] compositions as described in [3] or [4], above-mentioned R4aContaining 1 valency group shown in following formula (5):
(in formula (5),
W1And W2Identical or different, represent hydrogen atom, fluorine atom, trifluoromethyl, difluoromethyl or a methyl fluoride, 3 w3Respectively From representing hydrogen atom, fluorine atom or combinations thereof, W independently1、W2Or w3In, at least 1 be trifluoromethyl, difluoromethyl, One methyl fluoride or fluorine atom, m2 represents the integer of 0～9, and the maximum of carbon number contained in formula (5) is 10.〕.
[6] compositions as according to any one of [1]～[5], the ether compound described in [1] comprises dibutyl ethers, two different Amyl ether, diisobutyl ether or combinations thereof.
[7] compositions as according to any one of [1]～[6], the ether compound described in [1] is in the solvent described in [1] Shared ratio is 87 mass %～100 mass %.
[8] compositions as according to any one of [1]～[7], it comprises acid compound further.
[9] compositions as described in [8], above-mentioned acid compound is sulfoacid compound or sulfonate compound.
[10] compositions as described in [8], above-mentioned acid compound is salt system acid agent, halogen contained compound system acid agent Or sulfonic acid system acid agent.
[11] compositions as according to any one of [1]～[10], it comprises alkali compounds further.
[12] compositions as according to any one of [1]～[11], the resist being used together with above-mentioned composition is EUV (wavelength 13.5nm) uses resist.
[13] manufacture method of a kind of semiconductor device, it includes following operation: form the work of resist film on substrate Sequence；This resist film is coated with the resistant upper layer film formation compositions according to any one of [1]～[11] and dries Bake and form the operation of resistant upper layer film；The semiconductor substrate being coated to by this resistant upper layer film and resist film is carried out The operation of exposure；Carry out after exposure developing and removing this resistant upper layer film and the operation of resist film.
[14] manufacture method as described in [13], above-mentioned exposure utilizes EUV (wavelength 13.5nm) to carry out.
[15] forming method of a kind of Resist patterns for manufacturing semiconductor device, it includes in [1]～[11] Resistant upper layer film formation compositions described in any one is coated on the resist film being formed on semiconductor substrate goes forward side by side Row toasts and forms the operation of resistant upper layer film.
[16] a kind of method of resistant upper layer film formation compositions manufactured according to any one of [1]～[11], its The operation mixed including the ether compound using above-mentioned polymer (P) with as the carbon number 8～16 of solvent.
The effect of invention
The present invention relates to the compositions for forming resistant upper layer film, it combines as resistant upper layer film formation Thing, upper layer film formation compositions especially as EUV resist, do not mix with EUV resist, blocks when EUV exposes Undesirable exposure light such as UV, DUV and only selective transmission EUV, and may utilize developing liquid developing after exposure.
Further, the compositions of the present invention is contained by utilizing the aromatic series hydrocarbon ring wherein contained to absorb in EUV exposure light DUV light in the less desirable OOB of 180nm～260nm, it is possible to increase the resolving power of EUV resist.
During especially with the compositions of the present invention, in the case of the most in the polymer there is benzene ring structure, energy Enough it is formed near 200nm the resistant upper layer film with strong absorption.This resistant upper layer film except absorbing in addition to above-mentioned OOB, Also there is present in suppression lower floor the excessive of photoacid generator (Photo acid generator, PAG) present in resist The effect of activation.This effect makes Resist patterns deteriorate (such as LWR (live width in the excessive activation due to photoacid generator Roughness (Line Width Roughness)) value rise) time, it is possible to it is suppressed.
Particularly, in the case of it exists the photoacid generator of triphenylsulfonium system in EUV resist, effect is high.
And then, utilize the resistant upper layer film that the compositions of the present invention is formed particularly when EUV exposes, to from against corrosion The barrier of the degassing of agent is excellent, it is possible to prevent the pollution to exposure machine caused by degassing composition.
It addition, the resistant upper layer film formation compositions of the present invention is by using low molten of resist resin dissolubility The solvent (hereinafter also referred to ether series solvent) with ehter bond of agent, i.e. carbon number 8～16, goes for the anti-of various species Erosion agent, regardless of whether which kind of resist kind (eurymeric, minus) is.
Further, since the polymer (P) used in the present invention is containing the carboxyl brought by the cellular construction shown in formula (2), Therefore, in the case of common eurymeric resist, during development after exposure, alkaline development can be dissolved in together with resist Liquid, should in the case of, employ the compositions of this polymer (P) and may utilize alkaline-based developer and carry out dissolving and remove.By such just The developing process of type resist is referred to as PTD (Positive tone Development).
And then, the polymer (P) owing to using in the present invention can be dissolved in the developing process of common negative resist The development solvent (butyl acetate, 2-heptanone etc.) of middle use, therefore, it is possible to utilize this developer solution to carry out dissolving removing.By this The developing process of the negative resist of sample is referred to as NTD (Negative tone Development).
Detailed description of the invention
The resistant upper layer film formation compositions of the present invention contain polymer (P) and as solvent carbon number 8～ The ether compound of 16, described polymer (P) is containing the cellular construction shown in formula described later (1) and formula (2) and utilizes gel infiltration The weight average molecular weight that chromatograph (Gel Permeation Chromatography, GPC) method records is 500～2,000.
Detailed content about gel permeation chromatography describes in an embodiment.
Hereinafter the detailed content of the present invention is illustrated.
(resistant upper layer film formation compositions)
Being characterized mainly in that of the resistant upper layer film formation compositions of the present invention, containing polymer (P) with as molten The ether compound of the carbon number 8～16 of agent, described polymer (P) containing following formula (1) and the cellular construction shown in formula (2), And the weight average molecular weight utilizing gel permeation chromatography to record is 500～2,000.
In formula (1) or formula (2),
R1And R2Identical or different, represent hydrogen atom or the alkyl of carbon number 1～10,
Q1And Q2Identical or different, represent singly-bound, ester bond (-C (=O)-O-or-O-C (=O)-) or amido link (-NH-CO-or-CO-NH-),
X2Represent singly-bound, the alkylidene of carbon number 1～6 or the arlydene of carbon number 6～14,
R1aRepresent the alkyl of carbon number 1～10,
N1 represents the integer of 1～3, and m1 represents the integer of 0～2.
Cellular construction shown in formula (1) and formula (2) mol ratio overall relative to polymer (P) is preferably: relative to poly- Compound (P) is overall,
The construction unit of formula (1): 30～70 moles of %
The construction unit of formula (2): 20～50 moles of %.
The aromatic group that formula (1) is had absorbs the DUV light contained in above-mentioned EUV exposure light.Pass through R1aExistence, Dissolubility in ether series solvent improves.The carboxyl that formula (2) is had is to after by anti-aging drug, use when development In the case of alkaline aqueous solution, polymer (P) dissolves in alkaline aqueous solution and adds.
As the alkyl of carbon number 1～10, such as methyl, ethyl, n-pro-pyl, isopropyl, cyclopropyl, positive fourth can be enumerated Base, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-first Base-normal-butyl, 2-methyl-normal-butyl, 3-methyl-normal-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl- N-pro-pyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-pro-pyl, 1,1-diethyl-n-pro-pyl, cyclopenta, 1-first Base-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-Dimethyl-cyclopropyl, 2,3-dimethyl- Cyclopropyl, 1-ethyl-cyclopropyl base, 2-ethyl-cyclopropyl base, n-hexyl, 1-methyl-n-hexyl, 1-methyl-positive penta Base, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-normal-butyl, 1,2- Dimethyl-normal-butyl, 1,3-dimethyl-normal-butyl, 2,2-dimethyl-normal-butyl, 2,3-dimethyl-normal-butyl, 3, 3-dimethyl-normal-butyl, 1-ethyl-normal-butyl, 2-ethyl-normal-butyl, 1,1,2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-Ethyl-2-Methyl-n-pro-pyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-ring fourth Base, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-ring fourth Base, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-pro-pyl-ring Propyl group, 2-n-pro-pyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-ring Propyl group, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-Ethyl-2-Methyl-cyclopropyl, 2- Ethyl-1-methyl-cyclopropyl, 2-Ethyl-2-Methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, positive heptan Base, 1-methyl-n-heptyl, n-octyl, 1-methyl-n-octyl, n-nonyl, 1-methyl-n-nonyl and positive decyl etc..
As the alkylidene of carbon number 1～6, such as methylene, ethylidene, positive propylidene, isopropylidene, ring can be enumerated Propylidene, positive butylidene, isobutylene, sec-butylidene, tertiary butylidene, ring butylidene, 1-methyl-ring propylidene, 2-first Base-ring propylidene, positive pentylidene, 1-methyl-positive butylidene, 2-methyl-positive butylidene, 3-methyl-positive butylidene, 1,1-dimethyl-positive propylidene, 1,2-dimethyl-positive propylidene, 2,2-dimethyl-positive propylidene, 1-ethyl-just Propylidene, ring pentylidene, 1-methyl-ring butylidene, 2-methyl-ring butylidene, 3-methyl-ring butylidene, 1,2-bis- Methyl-ring propylidene, 2,3-dimethyl-ring propylidene, 1-ethyl-ring propylidene, 2-ethyl-ring propylidene, just Asia Hexyl, 1-methyl-positive pentylidene, 2-methyl-positive pentylidene, 3-methyl-positive pentylidene, 4-methyl-positive pentylidene, 1,1-dimethyl-positive butylidene, 1,2-dimethyl-positive butylidene, 1,3-dimethyl-positive butylidene, 2,2-diformazan Base-positive butylidene, 2,3-dimethyl-positive butylidene, 3,3-dimethyl-positive butylidene, 1-ethyl-positive butylidene, 2-ethyl-positive butylidene, 1,1,2-trimethyl-positive propylidene, 1,2,2-trimethyl-positive propylidene, 1-ethyl- 1-methyl-positive propylidene, 1-Ethyl-2-Methyl-positive propylidene, cyclohexylene, 1-methyl-ring pentylidene, 2-first Base-ring pentylidene, 3-methyl-ring pentylidene, 1-ethyl-ring butylidene, 2-ethyl-ring butylidene, 3-ethyl- Ring butylidene, 1,2-dimethyl-ring butylidene, 1,3-dimethyl-ring butylidene, 2,2-dimethyl-ring butylidene, 2, 3-dimethyl-ring butylidene, 2,4-dimethyl-ring butylidene, 3,3-dimethyl-ring butylidene, 1-n-pro-pyl-ring Propylidene, 2-n-pro-pyl-ring propylidene, 1-isopropyl-ring propylidene, 2-isopropyl-ring propylidene, 1,2,2-tri- Methyl-ring propylidene, 1,2,3-trimethyl-ring propylidene, 2,2,3-trimethyl-ring propylidene, 1-ethyl-2-first Base-ring propylidene, 2-ethyl-1-methyl-ring propylidene, 2-Ethyl-2-Methyl-ring propylidene and 2-ethyl- 3-methyl-ring propylidene etc..
As the arlydene of carbon number 6～14, such as phenylene, naphthylene, anthrylene, biphenylene can be enumerated.
For Q1And Q2For, it is preferred that identical or different, for singly-bound or ester bond (-C (=O)-O-or-O-C (=O)-).
R1And R2It is preferably selected from hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth Base or 1,1-diethyl-n-pro-pyl, further preferably selected from hydrogen atom, methyl or ethyl.
X2It is preferably singly-bound, methylene, ethylidene, positive propylidene, positive butylidene, phenylene or biphenylene.
R1aIt is preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, just Hexyl, 1-methyl n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, 1,1-diethyl-n-pro-pyl, 2-methyl- N-pro-pyl, 2,2 '-dimethyl-n-propyl.
For m1, reason based on above-mentioned record, from preventing the excessive work of photoacid generator present in resist From the viewpoint of changing thus forming the manufacturing cost of the viewpoint of good Resist patterns, polymer (P), preferably 0.
The ether compound that solvent is carbon number 8～16 (ether series solvent) used in the compositions of the present invention.Resist at EUV In erosion agent during coating resistant upper layer film, in order to prevent the mixing (mixing of layer) with EUV resist, as resistant upper layer film The solvent used in formation compositions, does not use the solvent used in usual EUV resist, and uses carbon number 8～16 The solvent (ether series solvent) with ehter bond be preferred.
The dissolubility of the above-mentioned ether series solvent resin to constituting resist is low, regardless of whether resin types (methacrylate System, PHS system, containing both mixing system etc. of methacrylate and hydroxy styrenes (HS)) which kind of is.
As in the compositions of the present invention use solvent, the ether compound (ether series solvent) of carbon number 8～16 as with Under formula (6) shown in.
A1-O-A2 (6)
In formula (6), A1And A2Represent the straight chain of carbon number 1～15, the side chain or ring-type that can be replaced independently of one another Saturated alkyl.
As straight chain, side chain or the ring-type saturated alkyl of carbon number 1～15, can enumerate such as methyl, ethyl, positive third Base, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl- Cyclopropyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, positive 13 Alkyl, n-tetradecane base, Pentadecane base, 1-methyl-normal-butyl, 2-methyl-normal-butyl, 3-methyl-normal-butyl, 1, 1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-pro-pyl, ring Amyl group, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-Dimethyl-cyclopropyl, 2, 3-Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl base, 2-ethyl-cyclopropyl base, n-hexyl, 1-methyl-n-pentyl, 2- Methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-normal-butyl, 1,2-diformazan Base-normal-butyl, 1,3-dimethyl-normal-butyl, 2,2-dimethyl-normal-butyl, 2,3-dimethyl-normal-butyl, 3,3- Dimethyl-normal-butyl, 1-ethyl-normal-butyl, 2-ethyl-normal-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2- Trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-Ethyl-2-Methyl-n-pro-pyl, cyclohexyl, 1-first Base-cyclopenta, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-pro-pyl-ring third Base, 2-n-pro-pyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-ring third Base, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-Ethyl-2-Methyl-cyclopropyl, 2-second Base-1-methyl-cyclopropyl, 2-Ethyl-2-Methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl etc..
As wherein preferred solvent, the dissolubility of polymer (P) and the harmony of the indissolubility of resist can be enumerated The dibutyl ethers of excellence, diisobutyl ether, di-tert-butyl ether, diamyl ether, diisoamyl ether, hexyl ether, dicaprylyl ether, ring Amyl methyl ether, as further preferred solvent, for dibutyl ethers, diisobutyl ether, diisoamyl ether, is particularly preferred to be Diisoamyl ether.These ether series solvents can be used alone or use as a mixture.
Ratio shared in above-mentioned ether solvents solvent in the present compositions is preferably 100 mass %, but also may be used Think 90 mass %～100 mass %, and then can also be 87 mass %～100 mass %.
The content of ether series solvent is the most, the highest with the mixing inhibition of resist.
It addition, in addition to above-mentioned ether series solvent, following alcohol series solvent or water can also be mixed as required.
Such as saturated alkyl alcohol, n-butyl alcohol, 2-butanol, isobutanol, the tert-butyl alcohol, 1-amylalcohol, 2-penta can be enumerated Alcohol, 3-amylalcohol, 1-heptanol, 2-enanthol, tert-pentyl alcohol, neopentyl alcohol, 2-methyl isophthalic acid-propanol, 2-methyl-1-butene alcohol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-3-amylalcohol, cyclopentanol, 1-hexanol, 2-hexanol, 3- Hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl Base-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene Alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-first Base-3-amylalcohol, 1-butoxy-2-propanol and Hexalin.
As aromatic alcohols, can enumerate 1-phenyl propanol, 2-phenyl propanol, 3-phenyl propanol, 2-phenyl phenol, Phenethanol, styracitol.
These alcohol series solvents or water can be used alone or two or more is applied in combination.Can be with relative to above-mentioned ether solvents For be that the ratio of 0.01～13 mass % contains other solvents above-mentioned.
It addition, from the standpoint of the convenience of the polymer (P) such as used from the synthesis present invention, except above-mentioned ether solvents Outside can also mix following organic solvent.As this solvent, such as, can use ethylene glycol monomethyl ether, ethylene glycol list second Base ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, carbiphene, propylene glycol, Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol propyl ether acetas, toluene, dimethylbenzene, Methylethyl Ketone, Ketocyclopentane, Ketohexamethylene, 2 hydroxypropionate, 2 hydroxyl 2 methylpropanoate, ethoxy ethyl acetate, hydroxyacetic acid Ethyl ester, 2 hydroxyl 3 methylbutanoic acid methyl ester, 3 methoxy methyl propionates, 3 methoxypropionate, 3 ethoxy-propionic acid second Ester, 3 ethoxypropanoate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate Deng.These organic solvents can be used alone or two or more is applied in combination.Can be with having relative to carbon number 8～16 It is that the ratio of 0.01～13 mass % contains other solvents above-mentioned for the solvent of ehter bond.
And then, above-mentioned polymer (P) preferably, in addition to containing formula (1) and formula (2), contains following the most further Cellular construction shown in formula (3).
In formula (3),
R3Represent hydrogen atom or the alkyl of carbon number 1～10,
Q3Represent singly-bound, ester bond (-C (=O)-O-or-O-C (=O)-) or amido link (-NH-CO-or- CO-NH-),
X3Represent singly-bound, the alkylidene of carbon number 1～6 or the arlydene of carbon number 6～14,
R3aIdentical or different, represent hydrogen atom, the alkyl of carbon number 1～10 or the acyl group of carbon number 1～4.
As the alkyl of carbon number 1～10, the alkyl of above-mentioned record can be enumerated.
As the alkylidene of carbon number 1～6, the alkylidene of above-mentioned record can be enumerated.
As the arlydene of carbon number 6～14, the arlydene of above-mentioned record can be enumerated.
As the acyl group of carbon number 1～4, formoxyl, acetyl group, propiono or bytyry can be enumerated.
R3It is preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, Particularly preferably hydrogen atom, methyl or ethyl.
Q3It is preferably singly-bound or ester bond (-C (=O)-O-or-O-C (=O)-).
X3It is preferably singly-bound, methylene, ethylidene, positive propylidene, positive butylidene.
R3aIt is preferably selected from hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth Base, 1-methyl-normal-butyl, 2-methyl-normal-butyl, 3-methyl-normal-butyl, 1-methyl-n-propyl, 2-methyl- Combination in n-pro-pyl, formoxyl or acetyl group.
The polymer (P) of the cellular construction with formula (3) utilizes the alkaline characteristic that its side chain has, and can carry out against corrosion The shape adjustment of agent.That is, by the bottom with the compositions of the present invention use resist present in acid interact, and Can be exposed development after resist shape control (expose, develop after resist preferably rectangular in shape).Comprise and contain Have the polymer (P) of the cellular construction of formula (3) though the compositions of the present invention add alkali compounds described later the most afterwards and straight Connect use, it is also possible to carry out good resist shape and control but it also may as required containing the unit knot with formula (3) The compositions of the polymer (P) of structure comprises alkali compounds further.
Therefore, the mol ratio that the cellular construction of formula (3) is overall relative to polymer (P) need not many, relative to polymer (P) being generally 0.1～50 mole of %, more preferably 0.1～30 mole of %, more preferably 0.1～20 mole of %, enters One step is preferably 0.1～10 mole of %.
Above-mentioned polymer (P) preferably, in addition to containing formula (1) and formula (2), contains following formula (4) the most further Shown cellular construction.
In formula (4),
R4Represent hydrogen atom or the alkyl of carbon number 1～10,
Q4Represent singly-bound, ester bond (-C (=O)-O-or-O-C (=O)-) or amido link (-NH-CO-or- CO-NH-),
R4aRepresent that alkyl or the hydrogen of part or all of carbon number that can be replaced by fluorine atoms 1～10 of hydrogen atom are former The aryl of part or all of carbon number 6～14 that can be replaced by this alkyl of son.
Herein, so-called " this alkyl ", refer to " the carbon number that part or all of hydrogen atom can be replaced by fluorine atoms The alkyl of 1～10 ".
As the alkyl of carbon number 1～10, the alkyl of above-mentioned record can be enumerated, a part for the hydrogen atom of this alkyl Or all can be replaced by fluorine atoms.
As the aryl of carbon number 6～14, phenyl, benzyl, naphthyl, anthryl, xenyl can be enumerated.
R4It is preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl or the tert-butyl group, Particularly preferably hydrogen atom, methyl or ethyl.
Q4It is preferably singly-bound or ester bond (-C (=O)-O-or-O-C (=O)-).
R4aThe organic group structure of 1 valency containing fluorine atom shown in following formula (5) of being preferably, single (trifluoromethyl) phenyl Or double (trifluoromethyl) phenyl.
Following formula (5):
In formula (5),
W1And W2Identical or different, represent hydrogen atom, fluorine atom, trifluoromethyl, difluoromethyl or a methyl fluoride, 3 w3Respectively From representing hydrogen atom, fluorine atom or combinations thereof, W independently1、W2Or w3In, at least 1 be trifluoromethyl, difluoromethyl, One methyl fluoride or fluorine atom, m2 represents the integer of 0～9, and the maximum of carbon number contained in formula (5) is 10.
Shown in the object lesson such as following formula (5-1) of the structure shown in formula (5)～formula (5-20).
Wherein, particularly preferred formula (5-1)～formula (5-7) or formula (5-15)～the structure shown in formula (5-17).
Cellular construction shown in formula (4) is to control the shape of resist and/or improving polymer (P) in above-mentioned ether system Dissolubility in solvent and add.Inventors herein have recognized that, particularly in the case of negative resist, by irradiating EUV light, by R4aThe shape of 2 electronic countermeasure erosion agent that shown side chain produces controls to be effective.
Using the compositions of the present invention as EUV resist upper layer film use time, the cellular construction shown in formula (4) contains fluorine Atom, but known fluorine atom absorbs EUV light.Polymer (P) the most undesirably contains the cellular construction of substantial amounts of formula (4).Formula (4) mol ratio overall relative to polymer (P), relative to polymer (P) be generally 0.1～40 mole of %, preferably 0.1～ 30 moles of %, more preferably 0.1～20 mole of %, more preferably 0.1～10 mole of %.
And then, for the compositions of the present invention, based on reason as described above, the most above-mentioned polymer (P) except Outside above-mentioned formula (1) and above-mentioned formula (2), contain the unit shown in above-mentioned formula (3) and above-mentioned formula (4) the most further Structure.
(manufacture method of polymer (P))
Hereinafter the method manufacturing the polymer (P) with cellular construction described above is described in detail.
The manufacture method of the polymer (P) used in the present invention includes following operation: make following formula (1-a) and formula (2- A) compound shown in is with the most preferred relative to polymer (P)
Compound shown in formula (1-a): 30～70 moles of %
Compound shown in formula (2-a): 20～50 moles of %
Ratio react in anti-solvent-applied.
In formula (1-a) or formula (2-a),
R1、R2、X1、X2、R1a, the definition of n1 and m1 and preferably scope as described above.
As the concrete example of the preferred compound shown in above-mentioned formula (1-a), formula (1-1)～formula (1-33) can be enumerated.
As the concrete example of the preferred compound shown in above-mentioned formula (2-a), formula (2-1)～formula (2-4) can be enumerated.
The manufacture method of polymer (P) comprises following operation as required: except above-mentioned formula (1-a) and above-mentioned formula (2- A), outside, also make the compound shown in following formula (3-a) and/or formula (4-a) with the most preferred relative to polymer (P)
Compound shown in formula (1-a): 30～70 moles of %
Compound shown in formula (2-a): 20～50 moles of %
Compound shown in formula (3-a) and/or formula (4-a): 0.1～40 mole of %
Ratio react in anti-solvent-applied.
In formula (3-a) or formula (4-a),
R3、R4、X3、X4、R3aAnd R4aDefinition and preferably scope as described above.
As the concrete example of the preferred compound shown in above-mentioned formula (3-a), formula (3-1)～formula (3-20) can be enumerated.
As the concrete example of the preferred compound shown in above-mentioned formula (4-a), formula (4-1)～formula (4-11) can be enumerated.
As the synthetic method of above-mentioned polymer (P), can enumerate as known acrylate copolymer or metering system The methods such as the radical polymerization of the synthetic method of acid polymer, anionic polymerisation, cationic polymerization.Described method can be known Polymerisation in solution, suspension polymerisation, emulsion polymerization, the various methods such as polymerisation in bulk.
As the polymerization initiator that uses during polymerization, it is possible to use 2,2 '-azo two (isopropyl cyanide), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '- Azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two (isopropyl cyanide), 1,1 '-azo two (hexamethylene-1-formonitrile HCN), 1-[(1-cyano group-1-Methylethyl) azo] Methanamide, 2,2 '-azo two [2-(2-imidazoline-2-base) propane] dihydrochloride, 2,2 '-azo two [2-(2-imidazoline- 2-yl) propane], 2,2 '-azo two (2-methyl-prop amidine) dihydrochloride etc..
The solvent used during as polymerization, it is possible to use dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, first Base cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, carbiphene, propylene glycol, propylene glycol list Methyl ether, propylene glycol monomethyl ether, propylene glycol propyl ether acetas, toluene, dimethylbenzene, methyl ethyl ketone, Ketocyclopentane, Ketohexamethylene, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxy-propionic acid second Ester, 3-ethoxypropanoate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, lactic acid fourth Ester etc..They can be used alone and can also be used in mixed way.
As the anti-solvent-applied of the polymer (P) in the compositions of the present invention, ethyl lactate is preferably used.
Reacted by the stirring carried out under the reaction condition of 50 DEG C～200 DEG C 1 hour～48 hours, it is possible to obtain this The polymer (P) of bright middle use.
The solution containing polymer (P) obtained as mentioned above is used directly for resistant upper layer film formation compositions Preparation.Alternatively, it is also possible to make polymer (P) bad molten at methanol, ethanol, ethyl acetate, hexane, toluene, acetonitrile, water etc. Precipitate and separate reclaim and use in agent or their mixed solvent.
As the precipitating solvent of the polymer (P) used in the present invention, water/methanol mixed solvent is preferably used.
By polymer (P) separate after, can directly in the solvent used by the compositions of the present invention re-dissolved and make With, it is possible to so that it uses the most again.Drying condition when being dried preferably utilizes baking oven etc. at 30～100 DEG C Carry out 6～48 hours.By polymer (P) reclaim after, can by its in above-mentioned ether series solvent re-dissolved and preparation cost invention Compositions, thus use as resistant upper layer film formation compositions.
In the present invention use polymer (P) utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) weight average molecular weight that method records changes according to the coating solvent used, solution viscosity etc., but changes with polystyrene Calculate for example, 500～2,000.When weight average molecular weight is less than 500, polymer (P) spreads in photoresist and makes The situation that lithography performance deteriorates.Weight average molecular weight is 2, and when more than 000, the polymer (P) dissolubility in above-mentioned ether solvents becomes Obtain insufficient, it is impossible to form the compositions of the stable present invention.It addition, the resistant upper layer film formed is used at photoresist Dissolubility in developer solution becomes insufficient, there is residue or poor visualization (film remaining and be unpatterned) occurs after development.
The content of the polymer (P) in the solid state component in above-mentioned composition is more than 20 mass %, such as 20 mass %～ 100 mass % or 30 mass %～100 mass %.The solid state component of the compositions of the present invention is 0.1～50 mass %, preferably 0.3 ～30 mass %.So-called solid state component is to eliminate composition obtained by solvent composition from resistant upper layer film formation compositions.
And then, the compositions of the present invention can comprise acid compound, alkali compounds, surfactant, rheology further Regulator etc..
For the resistant upper layer film formation compositions of the present invention, in order to exist with lower floor in photo-mask process The acidity of resist is consistent, can comprise acid compound further.Acid compound can use sulfoacid compound or sulfonic acid esterification Compound.Such as can coordinate double (4-hydroxy phenyl) sulfone, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, pyridine p-toluenesulfonic acid, water Acid compound and/or the 2,4,4,6-tetrabromo hexamethylenes two such as poplar acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxy benzoic acid The thermal acid generator such as ketenes, benzoin tosylate, 2-nitrobenzyl tosylat.Use level is that whole solid state component is every 100 mass % are 0.02～10 mass %, preferably 0.04～5 mass %.
For the resistant upper layer film formation compositions of the present invention, in order to exist with lower floor in photo-mask process The acidity of resist consistent, can add by exposure light that (such as ArF excimer laser irradiation, EUV irradiate, electronics is penetrated Line irradiation etc.) and produce the acid agent of acid.As preferred acid agent, such as, can enumerate double (4-tert-butyl-phenyl) iodine Salt system acid agent class, phenyl-bis-(the trichloromethyl)-s-triazine such as fluoroform sulphonate, triphenylsulfonium triflate sulfonate Deng sulfonic acid such as halogen contained compound system acid agent class, benzoin tosylate, N-hydroxy-succinamide triflate It it is acid agent class etc..The addition of above-mentioned acid agent be every 100 mass % of whole solid state component be 0.02～10 mass %, preferably It is 0.04～5 mass %.
The resistant upper layer film formation compositions of the present invention can comprise alkali compounds.By adding alkalescence chemical combination Thing, it is possible to carry out sensitivity adjusting during anti-aging drug.That is, the alkali compounds such as amine produces with by photoacid generator when exposure Acid reaction, the shaped upper part of the resist after development can be exposed by reducing the sensitivity of resist lower membrane Control (expose, develop after resist preferably rectangular in shape).
As alkali compounds, following known amines can be enumerated.
As amines, can enumerate ammonia, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, 2-(dimethylamino) ethanol, 2,2,2-trifluoroethylamine, 4-methyl morpholine etc..
Furthermore it is also possible to enumerate following shown aminobenzene compound.
The most such as there is the aminobenzene compound shown in formula (13-1).
In formula (13-1), U1～U5It is separately hydrogen atom, the alkyl of carbon number 1～10 or amino.
As the alkyl of carbon number 1～10, above-mentioned alkyl can be enumerated.
Wherein, preferably methyl, ethyl or isopropyl.
As above-claimed cpd, such as below formula (13-2)～formula (13-47) can be illustrated.
Furthermore it is possible to enumerate triethanolamine, three butanolamines, Trimethylamine, triethylamine, three n-pro-pyl amine, triisopropyl Amine, tri-n-butyl amine, tri-tert amine, three n-octylamine, triisopropanolamine, phenyldiethanol-amine, stearyl diethanolamine and The aromatic amines such as the tertiary amines such as diazabicyclooctane, pyridine and 4-dimethylaminopyridine.The most also can enumerate benzyl amine and The secondary amine such as the primary amine such as n-butylamine, diethylamide and di-n-butyl amine.These compounds can be used alone or more than two kinds groups Close and use.
In the compositions of the present invention, in addition to that mentioned above, it is also possible to add rheology control agent, surface the most further Activating agent etc..
Rheology control agent mainly adds with the purpose of the mobility of the compositions of the raising present invention.As concrete example, can Enumerate dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexylphthalate, neighbour The phthalic acid derivatives such as phthalic acid butyl isodecyl ester, Di-n-butyl Adipate, diisobutyl adipate, adipic acid two are different Adipic acid derivant, n-butyl maleate, ethyl maleate., the dinonyl maleates etc. such as monooctyl ester, adipic acid octyl group ester in the last of the ten Heavenly stems Oleic acid derivatives or n-butyl stearate, the stearic acid such as maleic acid derivatives, methyl oleate, butyl oleate, tetrahydrofurfuryl oleate The stearic acic derivatives such as glyceride.These rheology control agents are usual with overall 100 mass % relative to the compositions of the present invention Coordinate less than the ratio of 30 mass %.
In order to not produce pin hole, streak etc., improve the coating irregular to surface further, can in the compositions of the present invention With matching surface activating agent.As surfactant, can enumerate such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, Polyoxyethylene alkyl ether class, polyoxethylene octylphenyl phenol ether, the polyoxyethylene such as polyoxyethylene cetyl base ether, polyoxyethylene oleyl ether The polyoxyethylene alkylaryl ether classes such as nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers class, anhydrosorbitol list Laurate, sorbitan-monopalmityl ester, sorbitan monosterate, dehydrating sorbitol monooleate, Sorbitan fatty ester class, the polyoxyethylene such as anhydrosorbitol trioleate, anhydrosorbitol tristearate Sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan list The polyoxy second such as stearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic system surfactant, エ Off ト Star プ EF301, EF303, EF352 ((strain) ト such as alkene sorbitan fatty ester class ケ system プ ロ ダ Network Star system), メ ガ Off ア Star Network F171, F173 (big Japan イ Application キ (strain) system), Off ロ ラ De FC430, FC431 (Sumitomo ス リ エ system (strain) system), ア サ ヒ ガ De AG710, サ Off ロ Application S 382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (strain) system), Off タ ジ ェ Application ト シ リ ズ ((strain) ネ オ ス System) etc. fluorine system surfactant, organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) etc..These surface activitys The use level of agent is that every 100 mass % of all compositions of the compositions of the present invention are usually below 0.2 mass %, is preferably Below 0.1 mass %.These surfactants can individually add, and additionally can add with two or more combination.
(manufacture method of the resistant upper layer film formation compositions of the present invention)
Ether compound using above-mentioned polymer (P) with as the carbon number 8～16 of solvent mixes according to above-mentioned composition, example As being stirred mixing in room temperature～40 DEG C, it is possible to manufacture the resistant upper layer film formation compositions of the present invention.
(resist being used together with the compositions of the present invention)
For the resist being used together with the compositions of the present invention, it is possible to use KrF (wavelength 248nm) is with against corrosion Agent, ArF (wavelength 193nm) resist, EUV (wavelength 13.5nm) resist or EB (electron ray) use appointing in resist One, but preferably EUV (wavelength 13.5nm) resist or EB (electron ray) resist, further preferred EUV (wavelength 13.5nm) use resist.
If EUV (wavelength 13.5nm) resist, then as it has been described above, have OOB minimizing, the lithography performance of resist The excellent effect of raising, aerofluxus (outgas) minimizing etc..
The EUV resist being coated with as the lower floor of resistant upper layer film in the present invention, minus, eurymeric all can make With.There is the chemistry of the binding agent comprising acid agent and there is the group carrying out decomposing by acid and make alkali dissolution speed change Amplified corrosion-resisitng agent, comprise alkali-soluble binding agent and acid agent and carry out decomposing by acid and make the alkali dissolution speed of resist The chemically amplified corrosion-resisitng agent of the low molecular compound changed, comprise acid agent and have and carry out decomposing by acid and make alkali The binding agent of the group that dissolution velocity changes and carry out decomposing by acid and make the alkali dissolution speed of resist change Low molecular compound chemically amplified corrosion-resisitng agent, comprise to have and carry out decomposing by EUV and make alkali dissolution speed become The non-chemically amplified corrosion-resisitng agent of the binding agent of the group changed, comprise and have by EUV cut-off and make alkali dissolution speed send out The non-chemically amplified corrosion-resisitng agent etc. of the binding agent at the position of changing.
Such as the material system of EUV resist, have methacrylate ester, PHS system, containing methacrylate and hydroxyl Both mixing system etc. of base styrene (HS).
The present invention can use KrF resist or ArF resist.As under resistant upper layer film in the present invention KrF resist or ArF resist, negative type photoresist and the positive light anti-etching agent of layer coating all can use.Have and comprise Novolac resin and 1, the positive light anti-etching agent of 2-naphthoquinone diazido sulphonic acid ester, comprise to have and decomposed by acid And make binding agent and the chemical amplifying type photoresist of photoacid generator of the group that alkali dissolution speed rises, comprise and entered by acid Row decomposes and makes low molecular compound that the alkali dissolution speed of photoresist rises and alkali-soluble binding agent and photoacid generator Chemical amplifying type photoresist and comprise the bonding with the group carrying out decomposing and make alkali dissolution speed increase by acid Agent and carry out decomposing and the low molecular compound that makes the alkali dissolution speed of photoresist increase and the change of photoacid generator by acid Learn scale-up version photoresist etc..Such as ザ ダ ウ ケ ミ カ Le カ Application パ ニ (old ロ system ア Application De can be enumerated Ha ス electronic material (strain)) trade name APEX-E processed, Sumitomo Chemical (strain) trade name PAR710 processed and SHIN-ETSU HANTOTAI chemistry Industry (strain) trade name SEPR430 processed etc..Furthermore it is possible to enumerate such as ProC.SPIE, Vol.3999,330-334 (2000), In ProC.SPIE, Vol.3999,357-364 (2000) or ProC.SPIE, Vol.3999,365-374 (2000) described Such polymer system photoresist Han fluorine atom.
The present invention can use EB (electron ray) resist.Lower floor as resistant upper layer film in the present invention The electron ray resist of coating, negative type photoresist and positive light anti-etching agent all can use.In them, have and comprise product The chemical amplifying type of acid agent and the binding agent with the group carrying out decomposing by acid and make alkali dissolution speed change is against corrosion Agent, comprise alkali-soluble binding agent and acid agent and carry out decomposing by acid and make the alkali dissolution speed of resist change The chemically amplified corrosion-resisitng agent of low molecular compound, comprise acid agent and have and carry out decomposing by acid and make alkali dissolution speed send out The binding agent of the group of changing and carry out decomposing by acid and make that the alkali dissolution speed of resist changes degraded The chemically amplified corrosion-resisitng agent of compound, comprise there is the base carrying out decomposing by electron ray and make alkali dissolution speed change The non-chemically amplified corrosion-resisitng agent of the binding agent of group, comprise have by electron ray cut-off and make alkali dissolution speed become The non-chemically amplified corrosion-resisitng agent etc. of the binding agent at the position changed.Use the situation of these electron ray resists also can with will shine The source of penetrating is set to KrF, ArF light and employs the situation of photoresist and be identically formed Resist patterns.
The resistant upper layer film formed as having the resistant upper layer film formation compositions using the present invention is just The developer solution of type resist, it is possible to use sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia etc. are inorganic Secondary amine class, triethylamine, the methyidiethylamine such as the primary amine classes such as bases, ethylamine, N-propyl group amine, diethylamide, two-N-butylamines Etc. seasons such as the alcaminess such as tertiary amines, dimethylethanolamine, triethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline The aqueous solution of the bases such as cyclic amine such as ammonium salt, pyrroles, piperidines.Further can also in the aqueous solution of above-mentioned bases appropriate amount The surfactant adding alcohols, the nonionic systems etc. such as isopropyl alcohol uses.Wherein preferably developer solution is quaternary ammonium salt, enters one Step is preferably Tetramethylammonium hydroxide and choline.
(manufacture method of semiconductor device)
System to the semiconductor device of the present invention of the resistant upper layer film formation compositions employing the present invention below The method of making illustrates.
The present invention such as may be used for including the manufacture method of the semiconductor device of following operation: has formation transfer figure On the substrate of the processing object film of case, use or do not use EUV resist lower membrane, form the operation of EUV resist film；At this It is coated with the EUV resistant upper layer film formation compositions of the present invention on resist film and carries out toasting and being formed on EUV resist The operation of tunic；The operation of semiconductor-based board to explosure being coated to by this resistant upper layer film and resist film；Exposure After carry out developing and removing this resistant upper layer film and the operation of resist film.Exposure utilizes EUV (wavelength 13.5nm) to carry out.
The forming method of this resistant upper layer film is generally entered with land productivity method of spin coating as resist film formation etc. OK.Such as on Tokyo エ レ クトロン society spin coater, to processing object substrate, (such as silicon/silicon dioxide is coated to base Plate, glass substrate, ito substrate etc.) it is configured, this processing object substrate forms resist film, at processing object substrate On be coated with this resistant upper layer film formation compositions (varnish) with such as rotary rpm 200rpm～3000rpm, then utilize Heating plate is toasted 30～300 seconds at 50 DEG C～150 DEG C, forms this resistant upper layer film.The formation thickness of this resistant upper layer film For 3nm～100nm, or 5nm～100nm or 5nm～50nm.
As the resistant upper layer film formed dissolution velocity in photoresist developer solution, for 1nm per second with On, more than 3nm the most per second, more than 10nm the most per second.In the case of dissolution velocity is smaller, resistant upper layer Time required for the removing of film is elongated, causes productive reduction.Then suitable exposure light is utilized to carry out pattern formation After, use resist development liquid to develop, thus remove the not part of resist and this resistant upper layer film, formed against corrosion Agent pattern.
The semiconductor device of EUV resistant upper layer film formation compositions of the application present invention has on substrate shape successively Become the transfer processing object film of pattern, resist film and the composition of resistant upper layer film.This resistant upper layer film is by reducing base The harmful effect that substrate, EUV are brought, thus form the good Resist patterns of straight shape, it is possible to obtain sufficiently Allowance for EUV irradiation dose.In addition the resistant upper layer film of the present invention have the resist film that formed with lower floor equal or Its above big wet-etch rate, it is possible to held by alkaline-based developer etc. together with the not part of the resist film after exposure Change places removing.
In addition the processing object substrate of semiconductor device can be processed by arbitrary operation of dry ecthing, wet etching, logical Cross and use this resistant upper layer film such that it is able to using the Resist patterns that formed well as mask, by dry ecthing, wet corrosion Carve good shape transfer to processing object substrate.
The present invention such as may be used for including the manufacture method of the semiconductor device of following operation: there is formation transfer On the substrate of the processing object film of pattern, use or do not use KrF resist lower membrane, form the operation of KrF resist film；? It is coated with the KrF resistant upper layer film formation compositions of the present invention on this resist film and carries out toasting and forming KrF resist The operation of upper layer film；Operation by the semiconductor-based board to explosure coating by this resistant upper layer film and resist film；Exposure After carry out developing and removing this resistant upper layer film and the operation of resist film.Exposure is carried out by KrF.This resistant upper layer film Formed with above-mentioned EUV expose situation in the same manner as carry out.
The present invention such as may be used for including the manufacture method of the semiconductor device of following operation: there is formation transfer On the substrate of the processing object film of pattern, use or do not use ArF resist lower membrane, form the operation of ArF resist film；? It is coated with the ArF resistant upper layer film formation compositions of the present invention on this resist film and carries out toasting and forming ArF resist The operation of upper layer film；Operation by the semiconductor-based board to explosure coating by this resistant upper layer film and resist film；Exposure After carry out developing and removing this resistant upper layer film and the operation of resist film.Exposure utilizes ArF to carry out.This resistant upper layer film Formed with above-mentioned EUV expose situation in the same manner as carry out.
The present invention such as may be used for including the manufacture method of the semiconductor device of following operation: there is formation transfer On the substrate of the processing object film of pattern, use or do not use EB (electron ray) resist lower membrane, form electron ray and resist The operation of erosion agent film；This resist film is coated with the electron ray resistant upper layer film formation compositions of the present invention and carries out Toast and form the operation of electron ray resistant upper layer film；By the quasiconductor coating by this resistant upper layer film and resist film The operation that substrate is exposed；Carry out after exposure developing and removing this resistant upper layer film and the operation of resist film.Exposure profit Carry out with electron ray.Being formed of this resistant upper layer film is carried out in the same manner as the situation of above-mentioned EUV exposure.
(forming method of Resist patterns)
The present invention such as may be used for including the method forming Resist patterns of following operation: there is formation transfer On the substrate of the processing object film of pattern, use or do not use EUV resist lower membrane, form the operation of EUV resist film；? It is coated with the EUV resistant upper layer film formation compositions of the present invention on this resist film and carries out toasting and forming EUV resist The operation of upper layer film；Operation by the semiconductor-based board to explosure coating by this resistant upper layer film and resist film；Exposure After carry out developing and removing this resistant upper layer film and the operation of resist film.Exposure utilizes EUV to carry out.
The forming method of this resistant upper layer film is generally carried out with land productivity method of spin coating as resist film formation etc.. Such as on Tokyo エ レ クトロン society spin coater, to processing object substrate (such as silicon/silicon dioxide is substrate coated, Glass substrate, ito substrate etc.) be configured, on this processing object substrate formed resist film, on processing object substrate with Such as rotary rpm 200rpm～3000rpm is coated with this resistant upper layer film formation compositions (varnish), then utilizes heating Plate toasts 30～300 seconds with 50 DEG C～150 DEG C, forms this resistant upper layer film.The formation thickness of this resistant upper layer film is 3nm ～100nm or 5nm～100nm or 5nm～50nm.
As the resistant upper layer film formed dissolution velocity in photoresist developer solution, for 1nm per second with On, more than 3nm the most per second, more than 10nm the most per second.In the case of dissolution velocity is smaller, resistant upper layer film Time required for removing is elongated, causes productive reduction.Then utilize suitable exposure light to carry out after pattern formed, make Develop with resist development liquid, thus remove the not part of resist and this resistant upper layer film, form resist figure Case.
Even if above-mentioned forming method uses KrF, ArF, EB (electron ray) as exposure wavelength and to use KrF to use respectively Resist, ArF resist, EB (electron ray) are also possible as resist with resist.
Embodiment
Following synthesis example 1～the synthesis example 10 of this specification, compare synthesis example 1～compare the polymerization shown in synthesis example 6 The weight average molecular weight (Mw) of thing (P) is to utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) method The measurement result obtained.Measuring and use ソ Co., Ltd. GPC device, condition determination is as follows.It addition, this specification Following synthesis example shown in dispersion calculated by the weight average molecular weight measured and number-average molecular weight.
Determinator: HLC-8020GPC (trade name) (ソ Co., Ltd. system)
GPC post: TSKgel G2000HXL:2 root；G3000HXL:1 root；G4000HXL:1 root (trade name) is (all ソ Co., Ltd. system)
Column temperature: 40 DEG C
Solvent: oxolane (THF)
Flow: 1.0ml/ minute
Standard specimen: polystyrene (ソ Co., Ltd. system)
＜ synthesis example 1 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 7.16g (Tokyo chemical conversion work will be made Industry (strain) is made) it is dissolved in the solution of gained in ethyl lactate 182g and is heated to reflux.In solution after being heated to reflux, it is slowly added dropwise Azodiisobutyronitrile 1.71g (Tokyo chemical conversion industry (strain) system) is made to be dissolved in the solution of gained in ethyl lactate 78.0g, dropping After, it is heated to reflux making it react 24 hours in 160 DEG C, obtains the solution containing polymer (P-1).Make this reaction solution water/ Methanol mixed solvent 2, precipitates in 000g, 40 DEG C of drying under reduced pressure one nights, will obtain white poly-after the white solid that obtain filters Compound (P-1).It is to utilize the Weight-average molecular that polystyrene standard converts by the result that this polymer (P-1) carries out gpc analysis Amount is 1,200.Presumption polymer (P-1) has the structure of following formula (p-1).
＜ synthesis example 2 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and NIPA 2.82g (Tokyo chemical conversion industry (strain) system) be dissolved in gained in ethyl lactate 211g Solution be heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion industry (strain) makes) it is dissolved in the solution of gained in ethyl lactate 90.4g, after dropping, it is heated to reflux making it react 24 hours in 160 DEG C, Obtain the solution containing polymer (P-2).Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, by obtain After white-yellowish solid filters, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P-2).This polymer (P-2) is entered The result of row gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is 1,330.Presumption polymer (P-2) tool There is the structure of following formula (p-2).
＜ synthesis example 3 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and N-t-butylmethacrylamide 2.82g (Tokyo chemical conversion industry (strain) system) be dissolved in ethyl lactate 211g The solution of gained is heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion Industry (strain) system) it is dissolved in the solution of gained in ethyl lactate 90.4g, after dropping, it is heated to reflux making it react 24 in 160 DEG C little Time, obtain the solution containing polymer (P-3).Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, will After the white-yellowish solid that arrives filters, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P-3).To this polymer (P- 3) result carrying out gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is Isosorbide-5-Nitrae 60.Presumption polymer (P- 3) there is the structure of following formula (p-3).
＜ synthesis example 4 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and N tert butyl acrylamide 3.18g (Tokyo chemical conversion industry (strain) system) be dissolved in gained in ethyl lactate 213g Solution be heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion industry (strain) makes) it is dissolved in the solution of gained in ethyl lactate 91.3g, after dropping, it is heated to reflux making it react 24 hours in 160 DEG C, Obtain the solution containing polymer (P-4).Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, by obtain After white-yellowish solid filters, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P-4).This polymer (P-4) is entered The result of row gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is 1,750.Presumption polymer (P-4) tool There is the structure of following formula (p-4).
＜ synthesis example 5 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and N, N-DMAA 2.47g (Tokyo chemical conversion industry (strain) system) be dissolved in institute in ethyl lactate 208g The solution obtained is heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion work Industry (strain) is made) it is dissolved in the solution of gained in ethyl lactate 89.4g, after dropping, it is heated to reflux making it react 24 in 160 DEG C little Time, obtain the solution containing polymer (P-5).Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, will After the white-yellowish solid that arrives filters, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P).To this polymer (P-5) The result carrying out gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is 1,550.Presumption polymer (P-5) There is the structure of following formula (p-5).
＜ synthesis example 6 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and N, N-acrylamide 3.18g (Tokyo chemical conversion industry (strain) system) be dissolved in institute in ethyl lactate 213g The solution obtained is heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion work Industry (strain) is made) it is dissolved in the solution of gained in ethyl lactate 91.3g, after dropping, it is heated to reflux making it react 24 in 160 DEG C little Time, obtain the solution containing polymer (P-6).Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, will After the white-yellowish solid that arrives filters, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P-6).To this polymer (P- 6) result carrying out gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is 1,500.Presumption polymer (P- 6) there is the structure of following formula (p-6).
＜ synthesis example 7 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and acrylamide 1.77g (Tokyo chemical conversion industry (strain) system) be dissolved in ethyl lactate 204g the solution of gained in 160 DEG C are heated to reflux 24 hours.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion Industry (strain) system) it is dissolved in the solution of gained in ethyl lactate 87.5g, after dropping, it is heated to reflux making it react 24 hours, obtains Solution containing polymer (P-7).This reaction solution is made to precipitate in water/methanol mixed solvent 2000g, the HUANGBAI(sic) that will obtain After color solid filters, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P-7).This polymer (P-7) is carried out The result of gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is Isosorbide-5-Nitrae 70.Presumption polymer (P-7) has The structure of following formula (p-7).
＜ synthesis example 8 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and methacrylic acid 2,2,2-trifluoro ethyl ester 4.20g (Tokyo chemical conversion industry (strain) system) be dissolved in ethyl lactate In 219g, the solution of gained is heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (east Capital chemical conversion industry (strain) system) it is dissolved in the solution of gained in ethyl lactate 94.0g, after dropping, it is heated to reflux making it anti-in 160 DEG C Answer 24 hours, obtain the solution containing polymer (P-8).Make this reaction solution heavy in water/methanol mixed solvent 2,000g Form sediment, 40 DEG C of drying under reduced pressure one nights, white polymer (P-8) will be obtained after the white solid that obtain filters.To this polymer (P-8) result carrying out gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is 1,520.Presumption polymer (P-8) there is the structure of following formula (p-8).
＜ synthesis example 9 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and methacrylic acid 1,1,1,3,3,3-hexafluoro isopropyl ester 5.89g (Tokyo chemical conversion industry (strain) system) be dissolved in In ethyl lactate 230g, the solution of gained is heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion industry (strain) system) is dissolved in the solution of gained in ethyl lactate 98.7g, after dropping, heats back in 160 DEG C Stream makes it react 24 hours, obtains the solution containing polymer (P-9).Make this reaction solution at water/methanol mixed solvent 2, 000g precipitates, 40 DEG C of drying under reduced pressure one nights, white polymer (P-9) will be obtained after the white solid that obtain filters.Right This polymer (P-9) carries out the result of gpc analysis, and the weight average molecular weight utilizing polystyrene standard to convert is 1,950.Push away Determine polymer (P-9) and there is the structure of following formula (p-9).
＜ synthesis example 10 ＞
To make t-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), (Tokyo is melted into methacrylic acid 10.74g Industry (strain) system), NIPA 3.53g (Tokyo chemical conversion industry (strain) system) and methacrylic acid 1,1,1,3,3, 3-hexafluoro isopropyl ester 7.37g (Tokyo chemical conversion industry (strain) system) is dissolved in the solution of gained in ethyl lactate 277g and heats back Stream.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.31g (Tokyo chemical conversion industry (strain) system) be dissolved in The solution of gained in ethyl lactate 118g, after dropping, is heated to reflux making it react 24 hours in 160 DEG C, obtains containing polymer (P-10) solution.Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, the white-yellowish solid mistake that will obtain After filter, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P-10).This polymer (P-10) is carried out gpc analysis Result be that the weight average molecular weight utilizing polystyrene standard to convert is 1,680.Presumption polymer (P-10) has following formula (p-10) structure.
＜ compares synthesis example 1 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.60g (Tokyo chemical conversion work will be made Industry (strain) is made) and NIPA 2.82g (Tokyo chemical conversion industry (strain) system) be dissolved in gained in ethyl lactate 55g Solution be heated to reflux.In solution after being heated to reflux, it is slowly added dropwise and makes azodiisobutyronitrile 2.05g (Tokyo chemical conversion industry (strain) makes) it is dissolved in the solution of gained in ethyl lactate 23.4g, after dropping, it is heated to reflux making it react 24 hours in 160 DEG C, Obtain the solution containing polymer (P-11).Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, will obtain White-yellowish solid filter after, 40 DEG C of drying under reduced pressure one nights, obtain yellow-white polymer (P-11).To this polymer (P- 11) result carrying out gpc analysis is, the weight average molecular weight utilizing polystyrene standard to convert is 3,050.Presumption polymer (P- 11) there is the structure of following formula (p-11).
＜ compares synthesis example 2 ＞
T-butyl styrene 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid tertiary butyl ester 11.83g will be made (Tokyo chemical conversion industry (strain) system) is dissolved in the solution of gained in ethyl lactate 211g and is heated to reflux.Solution after being heated to reflux In, it is slowly added dropwise and makes azodiisobutyronitrile 1.71g (Tokyo chemical conversion industry (strain) system) be dissolved in gained in ethyl lactate 90.5g Solution, after dropping, is heated to reflux making it react 24 hours in 160 DEG C, obtains the solution containing polymer (P-12).Make this anti- Answer solution at water/methanol mixed solvent 2,000g precipitates, after the white solid obtained is filtered, in 40 DEG C of drying under reduced pressure one At night, obtain white polymer (P-12).It is to utilize standard polyphenyl second by the result that this polymer (P-12) carries out gpc analysis The weight average molecular weight of alkene conversion is 1,200.Presumption polymer (P-12) has the structure of following formula (p-12).
＜ compares synthesis example 3 ＞
4-vinyl benzoic acid 20.00g (ソ organic chemistry (strain) system), methacrylic acid 7.75g (Tokyo will be made Chemical conversion industry (strain) system) it is dissolved in the solution of gained in ethyl lactate 394g and is heated to reflux.In solution after being heated to reflux, slow Slow dropping makes azodiisobutyronitrile 1.87g (Tokyo chemical conversion industry (strain) system) be dissolved in gained in propylene glycol monomethyl ether 168.7g Solution, after dropping, be heated to reflux making it react 24 hours in 140 DEG C, obtain the solution containing polymer (P-13).Make this Reaction solution, at water/methanol mixed solvent 2, precipitates in 000g, after being filtered by the white solid obtained, in 40 DEG C of drying under reduced pressure one At night, obtain white polymer (P-13).It is to utilize standard polyphenyl second by the result that this polymer (P-13) carries out gpc analysis The weight average molecular weight of alkene conversion is 1,960.Presumption polymer (P-13) has the structure of following formula (p-13).
＜ compares synthesis example 4 ＞
Methacrylic acid tertiary butyl ester 20.00g (Tokyo chemical conversion industry (strain) system), methacrylic acid 8.07g (Tokyo will be made Chemical conversion industry (strain) system) it is dissolved in the solution of gained in ethyl lactate 82g and is heated to reflux.In solution after being heated to reflux, slow Slow dropping makes azodiisobutyronitrile 1.15g (Tokyo chemical conversion industry (strain) system) be dissolved in the solution of gained in ethyl lactate 35.1g, After dropping, it is heated to reflux making it react 24 hours in 160 DEG C, obtains the solution containing polymer (P-14).Make this reaction solution At water/methanol mixed solvent 2,000g precipitates, 40 DEG C of drying under reduced pressure one nights, will obtain after the white solid that obtain filters White polymer (P-14).It is to utilize polystyrene standard to convert by the result that this polymer (P-14) carries out gpc analysis Weight average molecular weight is 1,910.Presumption polymer (P-14) has the structure of following formula (p-14).
＜ compares synthesis example 5 ＞
By 1,5-dihydroxy naphthlene 3.5g (Tokyo chemical conversion industry (strain) system), (Tokyo is melted into 3,4-4-dihydroxy benzaldehyde 1.2g Industry (strain) system), double (trifluoromethyl) benzaldehyde 3.6g of 3,5-(Tokyo chemical conversion industry (strain) system), p-methyl benzenesulfonic acid one be hydrated Thing 0.43g (Tokyo chemical conversion industry (strain) system) joins in propylene glycol monomethyl ether 33.2g and dissolves.Reaction vessel is entered After the displacement of row nitrogen, make it react 4 hours in 140 DEG C, obtain the solution containing polymer (P-15).The solution obtained is added Methanol: in the solution of water=1:9, thus obtains dark brown polymer (P-15).The result carrying out gpc analysis is, the polymerization obtained The weight average molecular weight of thing is 2,830.Presumption polymer (P-15) has the structure of following formula (p-15).
＜ compares synthesis example 6 ＞
2,3,4,5,6-pentafluorostyrene 20.0g (Tokyo chemical conversion industry (strain) system), 4-vinyl benzoic acid will be made 1.70g (ソ organic chemistry (strain) system) is dissolved in the solution of gained in ethyl lactate 148g and is heated to reflux.It is being heated to reflux After solution in, be slowly added dropwise and make azodiisobutyronitrile 1.03g (Tokyo chemical conversion industry (strain) system) be dissolved in ethyl lactate 63.6g The solution of middle gained, after dropping, is heated to reflux making it react 24 hours in 160 DEG C, and obtain containing polymer (P-16) is molten Liquid.Make this reaction solution at water/methanol mixed solvent 2,000g precipitates, after the white solid obtained is filtered, subtract in 40 DEG C Press dried overnight, obtain white polymer (P-16).The result that this polymer (P-16) carries out gpc analysis is, utilizes mark The weight average molecular weight of quasi-polystyrene conversion is 1,400.Presumption polymer (P-16) has the structure of following formula (p-16).
＜ embodiment 1 ＞
Polymer (P-1) 0.6g obtained in above-mentioned synthesis example 1 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 2 ＞
Polymer (P-2) 0.6g obtained in above-mentioned synthesis example 2 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 3 ＞
Polymer (P-3) 0.6g obtained in above-mentioned synthesis example 3 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 4 ＞
Polymer (P-4) 0.6g obtained in above-mentioned synthesis example 4 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 5 ＞
Polymer (P-5) 0.6g obtained in above-mentioned synthesis example 5 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 6 ＞
Polymer (P-6) 0.6g obtained in above-mentioned synthesis example 6 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 7 ＞
Polymer (P-7) 0.6g obtained in above-mentioned synthesis example 7 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 8 ＞
Polymer (P-8) 0.6g obtained in above-mentioned synthesis example 8 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 9 ＞
Polymer (P-9) 0.6g obtained in above-mentioned synthesis example 9 adds diisoamyl ether 19.4g and dissolves. Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation combination Thing.
＜ embodiment 10 ＞
Polymer (P-10) 0.6g obtained in above-mentioned synthesis example 10 adds diisoamyl ether 19.4g and carries out molten Solve.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film formation group Compound.
＜ embodiment 11 ＞
In polymer (P-1) 0.6g obtained in above-mentioned synthesis example 1 add diisoamyl ether 17.46g, 4-methyl- 2-amylalcohol 1.94g also dissolves.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching and use Resistant upper layer film formation compositions.
＜ embodiment 12 ＞
In polymer (P-1) 0.6g obtained in above-mentioned synthesis example 1 add diisoamyl ether 16.49g, 4-methyl- 2-amylalcohol 2.91g also dissolves.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching and use Resistant upper layer film formation compositions.
＜ comparative example 1 ＞
Diisoamyl ether 17.46g, 4-is added in above-mentioned polymer (P-11) 0.6g comparing and obtaining in synthesis example 1 Methyl-2-amylalcohol 1.94g also dissolves.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make Photoetching resistant upper layer film formation compositions.
＜ comparative example 2 ＞
In above-mentioned polymer (P-12) 0.6g comparing and obtaining in synthesis example 2, add diisoamyl ether 19.4g and carry out Dissolve.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film and form use Compositions.
＜ comparative example 3 ＞
Diisoamyl ether 17.46g, 4-is added in above-mentioned polymer (P-13) 0.6g comparing and obtaining in synthesis example 3 Methyl-2-amylalcohol 1.94g also dissolves.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make Photoetching resistant upper layer film formation compositions.
＜ comparative example 4 ＞
In above-mentioned polymer (P-14) 0.6g comparing and obtaining in synthesis example 4, add diisoamyl ether 19.4g and carry out Dissolve.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film and form use Compositions.
＜ comparative example 5 ＞
In above-mentioned polymer (P-15) 0.6g comparing and obtaining in synthesis example 5, add diisoamyl ether 19.4g and carry out Dissolve.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film and form use Compositions.
＜ comparative example 6 ＞
4-methyl-2-amylalcohol 19.4g is added in above-mentioned polymer (P-16) 0.6g comparing and obtaining in synthesis example 6 And dissolve.Use the polyethylene microstrainer of aperture 0.05 μm to filter afterwards, make photoetching resistant upper layer film Formation compositions.
＜ comparative example 7 ＞
In above-mentioned polymer (P-11) 0.6g comparing and obtaining in synthesis example 1, add diisoamyl ether 19.4g and attempt Dissolve, but confirm polymer precipitation, it is impossible to obtain photoetching resistant upper layer film formation compositions.
＜ comparative example 8 ＞
In above-mentioned polymer (P-16) 0.6g comparing and obtaining in synthesis example 6, add diisoamyl ether 19.4g and attempt Dissolve, but confirm the precipitation of polymer, it is impossible to obtain photoetching resistant upper layer film formation compositions.
(resist insoluble validation test in ether series solvent)
Spinner is used to be coated with EUV Resist Solution (containing the resist of hydroxy styrenes (HS)).On hot plate Heat 1 minute at 100 DEG C, thus form resist film, carry out determining film thickness.
Use spinner by resistant upper layer film formation compositions solvent (dibutyl ethers, diisoamyl ether, two isobutyls Base ether) and the resistant upper layer film formation compositions of embodiment 1, embodiment 11 and embodiment 12 be coated on resist film On, on hot plate after 100 DEG C of heating 1 minute, (the feelings of resistant upper layer film formation compositions solvent on resist Under condition) or resistant upper layer film on (in the case of embodiment 1, embodiment 11 and embodiment 12) hold commercially available alkaline-based developer (Tokyo Applied Chemistry Industrial Co., Ltd.'s system, goods name: NMD-3) also places 60 seconds, makes it rotate with 3000rpm and uses Pure water carries out 30 seconds rinsing.After flushing, toast 60 seconds at 100 DEG C, carry out determining film thickness.
Judge that the film of resist reduces degree as was the case with table 1.The most nondecreasing for film information slip is shown as ◎, by enforcement No problem film decrement is expressed as zero.
[table 1]
The insoluble validation test of table 1 resist
(the applicable test to PTD technique)
Use spinner by the resist of preparation in embodiments of the invention 1～embodiment 9, comparative example 1 and comparative example 2 Tunic formation composition solution is coated on wafer, heats 1 minute at 100 DEG C on hot plate, forms resistant upper layer film, Carry out determining film thickness (thickness A: the thickness of resistant upper layer film).This resistant upper layer film holds commercially available alkaline-based developer (Tokyo Applied Chemistry Industrial Co., Ltd.'s system, goods name: NMD-3) also places 60 seconds, makes it rotate with 3000rpm and uses Pure water carries out 30 seconds rinsing.After flushing, toast 60 seconds at 100 DEG C, carry out determining film thickness (thickness B).Thickness B is the situation of 0nm It is lower it may be said that resistant upper layer film can be removed by developer solution.This represents that the compositions of the present invention can be used as PTD technique Resistant upper layer film application (table 2).
[table 2]
Table 2 determining film thickness
(the applicable test to NTD technique)
Spinner is used to be formed by the resistant upper layer film of preparation in embodiments of the invention 1～embodiment 10, comparative example 3 It is coated on wafer with composition solution, heats 1 minute at 100 DEG C on hot plate, form resistant upper layer film, carry out thickness Measure (thickness A: the thickness of resistant upper layer film).This resistant upper layer film holds acetic acid commonly used in NTD technique Butyl ester (solvent development liquid) also places 60 seconds so that it is rotate with 3000rpm.Afterwards, toast 60 seconds in 100 DEG C, carry out thickness survey Fixed (thickness C).It may be said that resistant upper layer film can be removed by solvent development liquid in the case of thickness C is 0nm.This represents this Bright compositions can apply (table 3) as NTD technique resistant upper layer film.
[table 3]
Table 3 determining film thickness
(optical parametric test)
Use spinner respectively by the resist of preparation in embodiments of the invention 1～embodiment 10, comparative example 4～6 Tunic formation composition solution is coated with on a quartz substrate.Heat 1 minute at 70 DEG C on hot plate, form resistant upper layer Film (thickness 30nm).Then, spectrophotometer resistant upper layer film mensuration wavelength 200nm～260nm to above-mentioned 10 kinds is used Absorbance.Absorbance during 13.5nm is calculated by simulation than the relation with film density by elementary composition.About DUV light Light-proofness, is more than 65% to be set to good by the maximum of the wavelength region absorbance at 200nm～260nm, sets less than 65% For bad.It addition, about the transmittance of EUV light (13.5nm), be set to the absorbance of more than 80% well, be set to less than 80% Bad.Formed by the resistant upper layer film of each embodiment the resistant upper layer film that obtains by compositions with by comparative example 4 and compare The resistant upper layer film that the resistant upper layer film formation compositions of example 5 obtains is compared, for the knot that the light-proofness of DUV light is excellent Really.Additionally, compared with forming, with by the resistant upper layer film of comparative example 6, the resistant upper layer film obtained by compositions, for EUV light The result (table 4) that transmittance is excellent.
[table 4]
Table 4EUV transmittance and DUV light-proofness
(resist aerofluxus inhibition test)
Using spinner to be coated with on silicon by EUV Resist Solution, heating 1 minute, is consequently formed on hot plate The resist film of thickness 60nm.Afterwards, use spinner to be formed by the resistant upper layer film of preparation in embodiments of the invention 2 to use Composition solution is coated on above-mentioned resist film, heats 1 minute at 70 DEG C on hot plate, is consequently formed the anti-of thickness 10nm Erosion agent upper layer film.By using resist aerofluxus monitor controller (EUVTechnology society EUV-PER1314) to this silicon wafer It is exhausted analysis (test example 1).Additionally, using do not form resistant upper layer film situation as test example 2.Need explanation It is, the solution that the use of EUV Resist Solution is more than the generation amount of the capacity in the case of the formation of common pattern.Will be by reality Execute the resistant upper layer film that the resistant upper layer film formation compositions of example obtains be applied to the situation on resist film upper strata with than The situation not applying resistant upper layer film of relatively example is compared, and capacity is greatly reduced.This represents that the compositions of the present invention can have The aerofluxus (table 5) that effect suppression is produced by resist.
[table 5]
Table 5 capacity (carbon pollution thickness)
(formation of Resist patterns and evaluation)
Using spinner to be coated with on silicon by EUV Resist Solution, heating 1 minute, is consequently formed on hot plate The resist film of thickness 50nm.Respectively preparation anti-in spin coating embodiments of the invention 1,2 and comparative example 5 on this resist film Erosion agent upper layer film formation compositions, heats 1 minute in 70 DEG C, uses EUV exposure device (Exitech society EUV Micro Exposure Tool (MS-13) exposes under conditions of NA=0.35, σ=0.36/0.68 [quadrupole (Quadrupole)] Light.After exposure, carry out PEB, be cooled to room temperature on the cooling plate, carry out developing and flushing process, form Resist patterns.By shape The target live width of the Resist patterns become is set to 26nm live width and spacing (line and space), observes the suitableeest light exposure and Jiao The Resist patterns of some position, carries out LWR (line width roughness (Line Width Roughness)) and compares (test example 3～6). Using do not form resistant upper layer film example as test example 6.Obtain being formed by the resistant upper layer film of embodiment by compositions To resistant upper layer film be applied to the situation on resist film upper strata and the situation phase not applying resistant upper layer film of comparative example Ratio, LWR greatly improves.This represents that the compositions of the present invention is suitable for forming Resist patterns (table 6).
[table 6]
Table 6LWR (line width roughness)
Industry utilizability
The present invention relates to not mix with resist, block when such as EUV exposes undesirable exposure light, such as UV, DUV and only selective transmission EUV, the EUV that can be used by the EUV lithography technique of developing liquid developing the most after exposure is against corrosion The resistant upper layer film formation compositions that photoetching process under agent upper layer film, other exposure wavelengths is used.

Claims (16)

1. a resistant upper layer film formation compositions, it comprises polymer (P) and the carbon number 8～16 as solvent Ether compound, described polymer (P) is containing the cellular construction shown in following formula (1) and formula (2) and utilizes gel permeation chromatography The weight average molecular weight recorded is 500～2,000,
In formula (1) or formula (2),
R1And R2Identical or different, represent hydrogen atom or the alkyl of carbon number 1～10,
Q1And Q2Identical or different, represent singly-bound, ester bond or amido link, wherein, described ester bond is-C (=O)-O-or-O- C (=O)-, described amido link is-NH-CO-or-CO-NH-,
X2Represent singly-bound, the alkylidene of carbon number 1～6 or the arlydene of carbon number 6～14,
R1aRepresent the alkyl of carbon number 1～10,
N1 represents the integer of 1～3, and m1 represents the integer of 0～2.
2. compositions as claimed in claim 1, described polymer (P) contains the cellular construction shown in following formula (3) further,
In formula (3),
R3Represent hydrogen atom or the alkyl of carbon number 1～10,
Q3Represent singly-bound, ester bond or amido link, wherein, described ester bond be-C (=O)-O-or-O-C (=O)-, described acyl Amine key is-NH-CO-or-CO-NH-,
X3Represent singly-bound, the alkylidene of carbon number 1～6 or the arlydene of carbon number 6～14,
R3aIdentical or different, represent hydrogen atom, the alkyl of carbon number 1～10 or the acyl group of carbon number 1～4.
3. compositions as claimed in claim 1, described polymer (P) contains the cellular construction shown in following formula (4) further,
In formula (4),
R4Represent hydrogen atom or the alkyl of carbon number 1～10,
Q4Represent singly-bound, ester bond or amido link, wherein, described ester bond be-C (=O)-O-or-O-C (=O)-, described acyl Amine key is-NH-CO-or-CO-NH-,
R4aRepresent the alkyl of part or all of carbon number that can be replaced by fluorine atoms 1～10 of hydrogen atom or hydrogen atom The aryl of the carbon number 6～14 that part or all can be replaced by this alkyl.
4. the compositions as according to any one of claims 1 to 3, described polymer (P) contains above-mentioned formula (3) and formula further (4) cellular construction shown in.
5. the compositions as described in claim 3 or 4, described R4aContaining 1 valency group shown in following formula (5),
In formula (5),
W1And W2Identical or different, represent hydrogen atom, fluorine atom, trifluoromethyl, difluoromethyl or a methyl fluoride, 3 w3The most solely On the spot represent hydrogen atom, fluorine atom or combinations thereof, W1、W2Or w3In, at least 1 is trifluoromethyl, difluoromethyl, a fluorine Methyl or fluorine atom, m2 represents the integer of 0～9, and the maximum of carbon number contained in formula (5) is 10.
6. the compositions as according to any one of Claims 1 to 5, the ether compound described in claim 1 comprises dibutyl Ether, diisoamyl ether, diisobutyl ether or combinations thereof.
7. the compositions as according to any one of claim 1～6, the ether compound described in claim 1 is in claim 1 Described in solvent in shared ratio be 87 mass %～100 mass %.
8. the compositions as according to any one of claim 1～7, it comprises acid compound further.
9. compositions as claimed in claim 8, described acid compound is sulfoacid compound or sulfonate compound.
10. compositions as claimed in claim 8, described acid compound is salt system acid agent, the product acid of halogen contained compound system Agent or sulfonic acid system acid agent.
11. compositionss as according to any one of claim 1～10, it comprises alkali compounds further.
12. compositionss as according to any one of claim 1～11, the resist being used together with above-mentioned composition is EUV With resist, the wavelength of described EUV is 13.5nm.
The manufacture method of 13. 1 kinds of semiconductor devices, it includes following operation: form the operation of resist film on substrate；? It is coated with the resistant upper layer film formation compositions according to any one of claim 1～11 on this resist film and toasts And form the operation of resistant upper layer film；The semiconductor substrate being coated to by this resistant upper layer film and resist film is exposed The operation of light；Carry out after exposure developing and removing this resistant upper layer film and the operation of resist film.
14. manufacture methods as claimed in claim 13, described exposure utilizes EUV to carry out, and the wavelength of described EUV is 13.5nm。
15. 1 kinds of forming methods being used for manufacturing the Resist patterns of semiconductor device, it includes to appoint in claim 1～11 One described resistant upper layer film formation compositions is coated on the resist film being formed on semiconductor substrate and carries out Toast and form the operation of resistant upper layer film.
The manufacture method of the resistant upper layer film formation compositions according to any one of 16. claim 1～11, it include by The operation that described polymer (P) and the ether compound as the carbon number 8～16 of solvent mix.
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